V. G. Kulichikhin

Viscoplasticity and stratified flow of colloid suspensions

Investigation of the rheology of concentrated colloid suspensions and direct observation of their flow allowed us to find several effects inherent to these media as typical soft matter. So, at low stress amplitudes, these colloids behave as mild gels with frequency independent elastic modulus and low mechanical losses. Meanwhile, suspensions demonstrate dualism of properties: at a given shear rate, they behave as viscoplastic media with clearly expressed yielding, while at a given low stress the pronounced Newtonian plateau is detected. The increase in shear rates and stresses leads to the sharp drop of the apparent viscosity, which usually is treated as the yielding effect. Transition through the yield stress is of a dynamic nature because the threshold stress depends on time and suspensions are thixotropic yielding materials. In the transient shear rate range, an unstable regime of deformation appears. It manifests itself either as deformation thickening up to jamming, or as the excitation of self-oscillations. The measuring of rheological properties in varying volume-to-surface ratio of a sample proves that flow of a suspension with high velocity at constant shear stress actually proceeds in a narrow layer inside the instrument gap. This conclusion has been confirmed by direct visual observations demonstrating that a flux is separated into three layers. A wide almost motionless layer is seen near a stationary surface. Near a moving surface, a narrow band with linear velocity profile is detected. Between them, a rather wide transient layer is observed and shear rate in this layer exceeds the average (global) shear rate by several times. Approximately, only a half of the total volume of a suspension is involved in flow. So, we observed a three-band flux of a suspension not described before. Shearing leads to an anisotropic structure of a solid phase.

The chaos-to-order transition in critical modes of shearing for polymer and nanocomposite melts

Two unusual experimental phenomena that were found for polymer melts or solutions containing the dispersed phases of Na-montmorillonite or detonation synthesis nanodiamond have been studied. These phenomena consist in the reduction of viscosity upon addition of specified amount of particles and in the formation of regular morphology by these particles in strong flows looking as a system of concentric rings. In other words, under certain conditions, there is transition to stratified shear stream and the viscosity of such a regular heterogeneous system canbe lower than that for the polymer matrix itself. Hence, both phenomena are mutually related; and the main problem here is the analysis of driving forces leading to the regular texture formation taking place in intense flows for unfilled viscoelastic polymers as well. As a preliminary explanation, the conception of the special kind of the elastic instability is discussed. This instability appears either in the regular helix-like structure formation or in the irregular elastic turbulence. The particles of the filler play a role of tracers that revealed the relief of texture.

Rheological properties of carbon black-filled blends of liquid-crystalline copolyester with thermoplastic polysulfone

Rheological properties of a two-phase polymeric blend containing LCCPE of poly(ethylene terephthalate) and p-hydroxybenzoic acid and thermoplastic polysulfone with varying concentrations of polymeric components and particulate filler have been studied. The theological behavior of such blends at different temperatures is governed by variation of the degree of ordering of LC-CPE macromolecules associated with the phase transition in the CPE at 260°C. Experimental results are discussed on the basis of concepts of compatibility of polymeric components in the melt or, if the system is incompatible, of the degree of interphase interaction between the components, as well as the impact of the filler and of the shear straining conditions on structurization in the system and compatibility. The filler exerts a compatibilizing effect on blend components, while the shear stress encourages the phase separation in the system. An extremal variation of viscosity of the LC-CPE/carbon black, silica and talk blends with the filler concentration on both at the flow in a uniform shear stress field and at the capillary flow has been found. Normalization of the filler concentration with respect to its specific surface yields a unified concentration dependence of the relative viscosity of LC-CPE filled with solid particles of various natures and specific surfaces.

Preparation of Polymer-Nanodiamond Composites with Improved Properties

An efficient method is developed to achieve improved dispersion of detonation nanodiamond particles in amorphous thermoplastic matrices. For an estimation of the nanodiamond distribution in slices, a method of optical and transmission electron microscopy is used. The complex set of mechanical properties of polymer-nanodiamond composites is considered: tensile properties, Izod impact strength and Brinell hardness. It is found that the reinforcing and toughening effects of uniformly-dispersed nanoparticles on polymer matrices is pronounced at lower loading compared with traditional mixing procedure.

A modern look on yield stress fluids

A concept of viscoplasticity advanced exactly one century ago by Bingham appears very fruitful because there are many natural and artificial materials that demonstrate viscoplastic behavior, i.e., they are able to pass from a solid to a liquid state under the influence of applied stress. However, although this transition was originally considered as a jump-like phenomenon occurring at a certain stress—the yield stress—numerous subsequent studies have shown that the real situation is more complicated. A long-term discussion about the possibility of flow at low stresses less than the yield stress came to today’s conclusion denying this possibility as being opposite to the existence of the maximal Newtonian viscosity in viscoelastic polymeric fluids. So, there is a contradiction between the central dogma of rheology which says that “everything flows” and the alleged impossibility for flow at a solid-like state of viscoplastic fluids. Then, the concept of the fragile destruction of an inner structure responsible for a solid-like state at the definite (yield) stress was replaced by an understanding of the yielding as a transition extending over some stress range and occurring in time. So, instead of the yield stress, yielding is characterized by the dependence of durability (or time-to-break) on the applied stress. In this review, experimental facts and the new understanding of yielding as a kinetic process are discussed. Besides, some other alternative methods for measuring the yield stress are considered.

Relaxation Properties of Pressure-sensitive Adhesives upon Withdrawal of Bonding Pressure

ABSTRACT Relaxation properties of pressure-sensitive adhesives (PSA) have been studied with the squeeze-recoil tester used in the regime of parallel-plate dilatometer under conditions imitating the removal of compressive force in the course of adhesive bond formation. The relaxation properties of PSAs are compared with their adhesive behavior measured using the 180-Deg Peel Test. Two classes of PSAs are considered: 1) conventional rubbery adhesives based on the mixtures of styrene-isoprene-styrene (SIS) block copolymer with a tackifier resin and a plasticizer, and butyl rubber plasticized with low-molecular-weight polyisobutylene, and 2) hydrophilic PSAs composed of the blends of high-molecular-weight poly(N-vinyl pyrrolidone) (PVP) with oligomeric polyethylene glycol (PEG). By comparing the adhesive and relaxation behaviors of different PSAs, the relaxation criteria for pressure-sensitive adhesion have been stated. Relaxation behavior of the examined PSAs demonstrates two values of retardation time: the shorter retardation time of 10–70 sec and the longer time of 300–660 sec. These times can be associated, respectively, with small- and large-scale mechanisms of strain recovery. By comparing the relaxation and adhesive properties of PVP-PEG blend (which involves the formation of a hydrogen-bonded network through both terminal hydroxyl groups in PEG short chains) with the properties of covalently crosslinked copolymers of vinyl pyrrolidone (VP) with PEG-diacrylate and comb-like VP copolymers with PEG-monomethacrylate, the contributions of covalent crosslinking and H-bonding network have been characterized.

Unusual rheological effects observed in polyacrylonitrile solutions

Unusual rheological effects have been revealed during the deformation of polyacrylonitrile (PAN) solutions in DMSO. The effects are observed during the study of rheological properties in a wide range of PAN concentrations and are explained by the structuring occurring at low polymer concentrations. At concentrations of at most 0.1%, the solutions exhibit the behavior of soft gels, which are characterized by yield stresses and frequency-independent storage moduli. As concentration is increased, both effects gradually vanish and the solutions are almost transformed into Newtonian liquids. The results have been explained by the formation of a supramolecular spatial structure at low polymer concentrations. As concentration is increased, the role of structuring is suppressed by the formation of a network of intermacromolecular entanglements. The ability of dilute PAN solutions to exist in two states, i.e., with destroyed structuring and in the form of a physical polymer gel, leads to stress self-oscillations and thixotropic effects. The addition of a precipitant (water) to the PAN-DMSO solutions leads to the formation of a gel throughout the concentration range.

Rheological properties of liquid crystalline polymer systems. Review

Abstract The viscous, viscoelastic and highly elastic properties of liquid crystalline solutions and melts of polymers are described. The main feature of the rheological behaviour of these systems is the dependence of the measured characteristics on the orientation of the preparation practically absent for isotropic systems. This leads to sharp change in the rheological properties on passing from the isotropic to the liquid crystalline state. Change in the mechanism of flow of anisotropic solutions and melts of polymers is particularly graphically manifest in presence of a fluidity limit and the existence of the viscosity maximum at a certain concentration and temperature. In addition, unusual effects for isotropic polymer systems observed in the liquid crystalline state are the negative value of the first difference in nornal stresses, the dependence of the rheological properties on the thermal and mechanical prehistory and the absence of a quantitative correlation between the resutls of dynamic and stationary shear experiments.

Rheology of carbosilane dendrimers with various types of end groups

The rheological properties of high-generation carbosilane dendrimers carrying different kinds of terminal groups are studied. It is shown that the nonlinear viscoelastic behavior of dendrimers and the high-temperature relaxation transition in dendrimers are interrelated and result from the reversible breakdown of the supramolecular structure formed by the system of contacts of exterior shells of dendrimers. The strength of the supramolecular structure is dependent on the specific interaction of terminal groups of dendrimers and their mobility. The dendrimers under study demonstrate the dualism of macromolecule-particle properties: They behave as both polymer melts and colloidal systems.

Self-assembly and elastic instability in polymer flows

This paper is devoted to the discussion of problems related to elastic instability arising in polymer flows. A new model of the rotary dynamics of macromolecules in shear fields of different geometries is proposed. The model is based on the nonlinear finite-difference Schrodinger equation describing the process of self-assembly for the system of bonded macromolecules as rotators. It is shown that the self-assembly of macromolecules is accompanied by the chaos-order transition that creates prerequisites for the flow elastic instability obeying the bifurcation mechanism. The self-assembly of macromolecules in shear fields is accompanied by the growth of the space scale in the molecular correlation and can lead to formation of rheological spiral and fibril superlattices.